Colored thermoplastic resin composition

ABSTRACT

A colored thermoplastic resin composition is provided which comprises a thermoplastic resin and a colorant in the form of an alkyleneoxy-substituted chromophore group provided in said thermoplastic resin in a minor amount sufficient to provide coloration to said thermoplastic resin. A process for preparing colored thermoplastic resins is also provided.

This is a continuation-in-part of application U.S. Ser. No. 877,056filed June 23, 1986, now U.S Pat. No. 4,732,570, which in turn is adivision of U.S. Ser. No. 775,614 filed Sept. 13, 1985, now U.S. Pat.No. 4,640,690.

The present invention relates to a colored thermoplastic resincomposition and to a process for preparing such compositions. Moreparticularly, the present invention relates to a thermoplastic resincomposition which has been colored by means of apolyalkyleneoxy-substituted chromophore group.

It is known that thermoplastic resin compositions may be colored by theaddition of dyes or pigments to the resin. Such dyes or pigments arecommonly used as dry powders, masterbatches, resin concentrates ordispersions in low molecular weight liquid carriers. Thermoplastic resincompositions which have been colored using pigments in particular may befrequently opaque and may lack the brilliance of color afforded by theuse of dyes. Also, considerably more pigment may ordinarily be requiredto achieve the same tinctorial strength as that which may be obtainedwith a dye. Use of pigments furthermore may give rise to problems withhandling, storage, incorporation, and color blending.

Certain of the deficiencies inherent in pigments, e.g.,dullness-of-color, low tinctorial strength, and undesired opacity incertain applications may be overcome by the use of polymer-soluble dyes.Thermoplastic resin compositions which have been colored usingpolymer-soluble dyes may thus afford products characterized by improvedclarity, brilliant colors, and high tinctorial strength. The use ofpolymer-soluble dyes, however, may lead to dye migration problems andeven solvent extraction of the dye from the colored thermoplastic resin.These problems may be particularly acute in low glass transitiontemperature, flexible resins such as polyethylene, polypropylene,plasticized polyvinyl chloride and other resins of a similar nature (SeePlastics Compounding 1984/85 Redbook, pp. 50-66; Modern PlasticsEncyclopedia, Colorants, 1984/85, p. 606). Due to these problems, theuse of polymer-soluble dyes may generally not be recommended in suchresins and few dyes are in fact recommended by their manufacturers foruse in such resin systems.

Attempts have been made to use polymeric dyes in the coloration ofthermoplastic resins. These dyes may, however, be difficult to make andmay also be difficult to incorporate into thermoplastic resins (as tomanufacture of these dyes see U.S. Pat. No. 4,477,635 to Mitra, assignedto 3M Corp.).

According to the present invention many of the problems associated withthe coloration of thermoplastic resins and many of the deficienciesassociated with prior art colored thermoplastic resin products may beobviated or overcome. Thus, as compared to conventional dyes, thecoloring agents which are employed according to the present inventiontypically may exhibit a significantly and surprisingly diminishedtendency toward color migration and solvent extraction of the colorantfrom the thermoplastic resin. These observations are especiallynoticeable in those resins having a generally low glass transitiontemperature such as certain polyolefins, polyvinyl chloride and othersimilar resins. Furthermore, as compared to pigments and possibly evensome conventional dyestuffs, improved clarity and tinctorial strengthmay also be achieved.

Lastly, the coloring agents employed in the thermoplastic resincompositions of the present invention may be provided, if desired, inthe liquid phase at ambient conditions of temperature and pressure(although the invention is certainly not limited to liquid phasecolorants). Because they may be in the liquid phase, they may providemany processing advantages during actual use, including improvedhandling, storage, incorporation and color blending.

Accordingly, the present invention provides a colored thermoplasticresin composition which comprises a thermoplastic resin and a colorantin the form of a polyalkyleneoxy-substituted chromophore group providedin said thermoplastic resin in a minor amount sufficient to providecoloration to said thermoplastic resin.

Thermoplastic resins which may be used according to the presentinvention include a wide range of synthetic resins and synthetic resincompositions which are known in the art as being essentiallythermoplastic in nature. The term "thermoplastic" is used herein in itsconventional sense to mean a resin "having the property of softening orfusing when heated and of hardening again when cooled" (see Webster'sSeventh Collegiate Dictionary, G & C Merriam Co., 1965). Thermoplasticresins are to be clearly distinguished both in terms of their essentialphysical and chemical characteristics from thermosetting resins. Theterm "thermosetting" as used herein is also used in its conventionalsense to mean a resin "having the property of becoming permanently rigidwhen heated or cured.

Examples of thermoplastic resin systems which may be employed include awide range of polyolefin polymers, e.g., polyethylene, linear lowdensity polyethylene, polypropylene, polybutylene and copolymers madefrom ethylene, propylene and/or butylene. Other thermoplastic polymerswhich may be employed according to the present invention includepolyvinyl chloride, polyvinylidene chloride, cellulosic resins such ascellulose acetate, cellulose acetate butyrate and cellulose acetatepropionate, acrylic resins such as polymethyl methacrylate, styreneacrylonitrile, polystyrene, polycarbonate andacrylonitrile-butadiene-styrene (herein ABS), polyamides such as nylon 6and nylon 66 and polyesters such as polyethylene terephthalate,especially glycol modified polyethylene terephthalate and polybutyleneterephthalate.

As mentioned above, the thermoplastic resins of the present inventionare provided with coloration. The colorants may be most broadlydescribed as polyalkyleneoxy-substituted chromophore groups. Colorantsof this general type have found use in the past as fugitive tints asdisclosed in U.S. Pat. No. 3,157,663 to Kuhn (incorporated byreference). Other colorants which may be employed according to thepresent invention include the alkaline-stable colorants of thetriphenylmethane type as described in U.S. Pat. No. 3,927,044(incorporated by reference).

Yet another category of colorants which may be employed in thecomposition and process of the present invention are the ester cappedpolyalkyleneoxy colorants disclosed in U.S. Pat. No. 4,167,510(incorporated by reference). Such colorants comprise an organicchromophore group having from 1 to 5 capped polyalkyleneoxy unitswherein the total of alkyleneoxy units in the molecule are from 2 toabout 300. The alkylene moiety of the polyalkyleneoxy units containsfrom 2 to about 4 carbon atoms. The properties of the colorants may bevaried depending upon the particular capping moiety employed, thepresence or absence of at least one ionic group and the total number ofalkyleneoxy units present in the colorant.

Still another category of colorants which may be employed according tothe present invention includes those disclosed in U.S. Pat. No.4,400,320, Keller, et al. (incorporated by reference). Such colorantsmay be characterized by the formula: ##STR1## wherein R is selected frommeta-toluidene, meta-aminophenol, aniline or dimethoxyaniline; A isselected from N, O, S or CO₂ ; the alkylene group of the alkyleneoxyconstituent contains from 2 to about 4 carbon atoms; n is an integer offrom 2 to about 300; m is 1 when A is O, S, or CO.sub. 2, and 2 when Ais N; x is an integer of from 1 to about 5; and the product of n m x isfrom 2 to about 400.

More recently, colorants of the general type employed in the presentthermoplastic resin compositions have found utility in the coloration ofthermosetting resins as described in Cross, et al., U.S. Pat. No.4,284,729. Significantly with regard to the Cross, et al. discovery, thecolorant is chemically bound to the polymer molecule, typically duringthe polyaddition reaction by means of which the thermosetting polymer isformed. In addition the colorants of Cross, et al. hve been generallyconsidered to be of a type which is "chemically compatible" with thepolymer or resin environment. By contrast, the colorants according tothe present invention are actually incorporated into a resin systemcomprised of preformed polymers so that there are essentially noreactive groups by means of which the colorant could become chemicalybound to the polymer molecules. Polyalkyleneoxy-substituted chromophoregroups, furthermore, have heretofore been considered by those mostfamiliar with the properties of such colorants to be essentiallyincompatible with certain thermoplastic resin system environments which,in the case for instance of polyolefins, are typically non-polar orhydrophobic environments. It is, therefore, all the more surprising thatsuch colorants, which by virtue of their polar, polyalkyleneoxy groupsare generally hydrophilic in nature, find utility in the coloration ofsuch thermoplastic resin systems.

The chromophore group of the colorant may vary widely, and may includecompunds characterized in the art as dyestuffs or as pigments. Theactual group used will depend to a large extent upon, for instance, thedesired color and colorfastness characteristics. The chromophore groupmay be attached to at least one polyalkyleneoxy-substitutent through asuitable linking moiety such as nitrogen, oxygen, sulfur, etc. Examplesof chromophore groups include nitroso, nitro, azo (including monoazo,disazo, trisazo, tetrakisazo, polyazo, formazan, azomethine and metalcomplexes thereof), stilbene, diarylmethane, triarylmethane, xanthene,acridine, quinoline, methine (including polmethine), thiazole, indamine,indophenol, azine, thiazine, oxazine, aminoketone, hydroxyketone,anthraquinone (including anthrapyrazolines, anthrone, anthrapyridone,anthrapyrimidine, flavanthrone, pyranthrone, benzanthrone, perylene,perinone, naphthalimide and other structures formally related toanthraquinone), indigoid (including thioindigoid), and phthalocyaninechromophore groups. Particularly useful in the preparation of thecolorants used in the compositions of the invention may be the azo,anthraquinone, triarylmethane and methine dyestuff radicals.

The chromophore group of the colorants employed in the compositions ofthe present invention may be substituted with at least onepolyalkyleneoxy group. Typical of such groups which may be attached tothe chromophore group are the polymeric eposides, such as thepolyalkylene oxides and copolymers thereof. Typical polyalkylene oxidesand copolymers of same which may be employed to provide the colorantsinclude those made from alkylene oxide monomers containing from one toabout four carbon atoms. Examples include polyethylene oxides,polypropylene oxides, polybutylene oxides, copolymers of polyethyleneoxides, polypropylene oxides and polybutylene oxides, and othercopolymers including block copolymers, in which a majority of thepolymeric substituent is polyethylene oxide, polypropylene oxide and/orpolybutylene oxide. Further, such polyalkyleneoxy group may have anaverage molecular weight in the range of from about 132 to about 10,000,preferably from about 176 to about 5000.

It is to be understood that because the colorants may not ordinarily bechemically bound to the thermoplastic polymer, the precise chemicalidentity of the end group on the polyalkyleneoxy group may not becritical insofar as the proper functioning of the colorant is concernedin the composition. With this consideration in mind certain mostpreferred colorants will be defined where certain end groups will beidentified. Such recitation of end groups is not to be construed aslimiting the invention in its broader embodiments in any way. Accordingto such a most preferred embodiment the colorants may be characterizedas follows:

    R A[(alkyleneoxy constituent).sub.n R.sub. 1].sub.m x

wherein R-A is an organic chromophore group, A is a linking moiety insaid organic chromophore group selected from the group consisting of N,O, S or CO.sub. 2, the alkylene moiety of the alkyleneoxy constituentcontains from 2 to about 4 carbon atoms, n is an integer of from 2 toabout 230, m is 1 when A is O, S, CO₂ and 1 or 2 when A is N, x is aninteger of from 1 to 5, and the product of n times x times m (n m x) isfrom 2 to about 230, and R.sub. 1 is a member of the group consisting of##STR2## and sulfonates and sulfates of each of the members of saidgroup, wherein R₂ is H, an alkyl radical containing up to about 20carbon atoms or carboxy-terminated alkyl radical containing up to about20 carbon atoms, j and k are OH, OM or OR₃ wherein M is a cation moietyof an alkali metal, an alkaline earth metal, transition metal, e.g.,nickel, etc. or ammonium, and R₃ is an alkyl radical containing up toabout 20 carbon atoms.

As mentioned above, the colorants may be employed in the thermoplasticresins in a minor amount sufficient to provide the desired degree ofcoloration in the resin. The actual amount used will, in addition to thedesired depth of shade, depend upon the tinctorial strength of thechromophore used and the overall molecular weight of the colorant, e.g.,chromophore plus polyalkyleneoxy chain length. Typiclly the amount ofcolorant employed may be from abut 0.0001 percent to about 5 percent,preferably from about 0.001 percent to about 3 percent, by weight basedupon the overall weight of the resin composition.

Other conventional additives may also be present in the resincompositions of the present invention. For instance, such additives mayinclude plasticizers, antioxidants, stabilizers, lubricants, flameretardants, nucleating agents and other additives which will be readilyidentified by those skilled in the art. In general, the colorants havebeen observed to have little or no adverse interactions with theseconventional additives.

Because the colorants if used properly ordinarily do not detract fromthe clarity of the resin, it has been found that additives which improvethe clarity of such resins may be particularly desirable for use incombination with colorants as described herein to provide resin productsthat are both colored and which also have excellent clarity. Oneparticular class of additives which have been found to be useful in thisregard are the benzylidene sorbitols including substituted benzylidenesorbitols such as those described in U.S. Pat. No. 4,016,118 to Hamada,et al. (E. C. Chemical); U.S. Pat. No. 4,371,645 to Mahaffey (MillikenResearch Corporation); and Japanese Patent Number SHO [1977]53-117044 toKobayashi, et al. (New Japan Chemical); all of these patents beinghereby incorporated herein by reference.

Any suitable procedure may be employed to produce the colorants of theinvention whereby the polyalkyleneoxy group, or groups, are coupled to achromophore group. For example, the procedure set forth in U.S. Pat. No.3,157,663, hereby incorporated by reference, may be employed. Theparticular shade of the colorant will depend primarily upon theparticular chromophore group selected. A large variety of colors andshades may be obtained by blending two or more colorants. Blending ofthe colorants of the present invention can be readily accomplished asthe colorants are polymeric materials which may have substantiallyidentical solubility characteristics, which are dictated by the natureof the polymeric chain. Therefore, the colorants are in general solublein one another, and are also in general completely compatible with eachother.

For example, the colorants of the invention may be prepared byconverting a dyestuff intermediate containing a primary amino group intothe corresponding polymeric compound and employing the resultingcompound to produce a compound having a chromophoric group in themolecule. In the case of azo colorants, this may be accomplished byreacting a primary aromatic amine with an appropriate amount of analkylene oxide or mixtures of alkylene oxides, such as ethylene oxide,propylene oxide, or even butylene oxide, according to procedures wellknown in the art, and then coupling the resulting compound with adiazonium salt of an aromatic amine. In order to prepare colorants ofthe triarylmethane class, aromatic amines that have been reacted asstated above with an alkylene oxide are condensed with aromaticaldehydes and the resulting condensation products are oxidized to formthe triarylmethane colorants. While azo, methine, triarylmethane andanthraquinone colorants are preferred because of their ease ofpreparation and brilliance of color as well as the multitude of shadesavailable, many other colorants may be prepared by known procedures.

According to the process of the invention, the colorant may beincorporated into the thermoplastic resin using conventional techniquessuch as those employed to incorporate other additives in such resins.For instance, the colorant may be incorporated into the resin by simplyadding it to the resin while the resin is in a plasticized or moltenstate, typically prior to formation of the polymer into its final shape,e.g., by molding, extrusion, blow-molding and the like. For instance,when the thermoplastic resin to be colored is a polyolefin resin theprocess may be carried out by adding a colorant comprised of apolyalkyleneoxy-substituted chromophore group directly to the moltenpolymer, by tumbling it onto a pre-extruded pelletized resin, or bymixing it into the resin powder prior to extrusion. The polymer may thenbe molded or extruded in the usual manner, i.e., in the same way as forpolyolefin resins which are not colored. Details about these proceduresmay be found in the relevant literature.

Alternatively, a concentrate of the colorant in an appropriate resin orvehicle may first be prepared. Such concentrate may contain anappropriately high percentage of colorant. The concentrates may be inthe form of liquids, solids, e.g., powders, pellets, etc., as may bedesired. These concentrates may then be incorporated into thethermoplastic resin as is well understood in the art.

As will be well understood by those skilled in the art, the colorant maybe incorporated into the thermoplastic resin by any of a wide varietyalternative techniques including, for instance, first dissolving thethermoplastic resin in a suitable solvent for the resin, incorporatingthe colorant into the solution of the thermoplastic resin and thenevaporating the solvent whereby the colorant will become distributedthroughout the mass of the thermoplastic resin. It has been found, forinstance, that such technique for incorporating the colorant into theresin may be particularly advantageous where coloration is to beprovided in films or laminates. In addition, thermoplastic resins havefound wide utility in ink formulations and the colorants of the presentinvention may be conveniently incorporated into the final thermoplasticresin ink by incorporating it into the ink composition, which isessentially the dissolved thermoplastic resin in a suitable solventvehicle together with an appropriate quantity of a colorant as describedherein.

The colorants used in the process and in the composition of the presentinvention are polymeric colorants which may according to one embodimentbe in the liquid phase. Thus, if in the liquid phase, they may be addedto the thermoplastic polymer melt in solvent-free form rather than inthe form of solutions or dispersions in a suitable solvent or dispersingmedium. Obviously liquids may have certain processing advantages oversolids; and moreover liquids may, if desired, be added directly to themolten polymer and therefore contain no extraneous solvent or dispersingagents. This process may, therefore, provide unusual and advantageousproperties in the final thermoplastic resin product. Alternatively,however, the colorants may be premixed with minor amounts of a solventor dispersing agent which is compatible with the resin, thus providingcertain processing advantages.

The following examples illustrate the invention, but are not to beconstrued as limiting the invention which is defined in the claimsappended hereto. The parts and percentages, unless otherwise indicatedare all by weight.

EXAMPLE 1

One hundred and sixty-five and four tenths parts of2-chloro-4(methylsulfone)aniline were added to a cold (less than 40° C.)mixture of 205.5 parts of 70% sulfuric acid and 535 parts water. One andsix tenths parts of 2-ethylhexanol were added followed by the slowaddition of 370.5 parts of 40% nitrosyl sulfuric acid. The temperaturewas maintained at less than 0° C. during the addition by use of a dryice/isopropanol bath. The solution was stirred about 1.5 hours. Excessnitrite was then destroyed by slow additions of a total of 10 parts ofsulfamic acid. The absence of nitrite was determined by the use ofstarch-iodide indicator paper. The resulting yellow solution contains0.627 millimoles per gram of active diazonium salt and was maintained ata temperature less than 0° C. until used.

Thirty-one and five tenths millimoles of the ten mole ethoxylate ofaniline were mixed with 50 parts of water. Thirty millimoles (47.8parts) of the above described diazo solution were then slowly added withstirring. The temperature was maintained at 20°-30° C. by the additionof crushed ice. The solution was allowed to stand for at least one hourand then neutralized by the addition of 50% aqueous sodium hydroxide.The mixture thus obtained was extracted with 50 milliliters of methylenechloride. The methylene chloride extract was washed twice with equalportions of water and the methylene chloride then removed under reducedpressure to afford the product.

Using the general procedure described above, a series of relatedcolorants were prepared. A generalized structure for the colorants isset forth below and the colorants are more specifically defined inTables 1 and 2 below: ##STR3## wherein R₁ -R₅ are set forth in Tables 1and

Liquid products were isolated by extraction with 50 milliliters ofmethylene chloride. The methylene chloride extract was washed twice withan equal portion of water and then evaporated to dryness under reducedpressure to afford the product. Crystalline products were isolated byfiltration, washed with water, and then recrystallized fromethanol/water.

The colorants listed in Table 1 were prepared in order to provide acomparison between the colorants used in the composition of thisinvention (runs 1 through 17) and their conventional dyestuffequivalents which are runs 18 through 21 in Table 2. The colorantscontained in Table 1 are all liquids at ambient temperature while thoselisted in Table 2 are solids. The comparative data is set forth inExamples 10 and 16 below.

The following abbreviations are utilized in the following tables:EO=ethylene oxide; PO=propylene oxide; Et =ethyl; Ac=acetyl. Also wherenumbers are separated by diagonals, e.g., 2/15/5, such refers to molesEO/ moles PO/ moles EO. Unless otherwise indicated, the polyalkyleneoxygroups are hydroxyl terminated.

                  TABLE 1                                                         ______________________________________                                                                               Average                                Run                                    Molecular                              Number  R.sub.1  R.sub.2                                                                              R.sub.3                                                                            R.sub.4 R.sub.5                                                                         Weight                                 ______________________________________                                        1       CH.sub.3 SO.sub.2                                                                      Cl     H    4EO       485                                    2       "        "      "    2EO/2PO   513                                    3       "        "      "    2EO/4PO   629                                    4       "        "      "    2EO/6PO   745                                    5       "        "      "    10EO      749                                    6       "        "      CH.sub.3                                                                           "         763                                    7       "        "      H    2EO/8PO   861                                    8       "        "      CH.sub.3                                                                           2/5/5     921                                    9       "        "      H    2EO/10PO  977                                    10      "        "      "    2/10/3    1109                                   11      NO.sub.2 H      "    20EO      1120                                   12      CH.sub.3 SO.sub.2                                                                      Cl     CH.sub.3                                                                           2/10/3    1123                                   13      "        "      "    2/10/6    1255                                   14      "        "      H    2/15/5    1487                                   15      "        "      CH.sub.3                                                                           2/14/8    1575                                   16      "        "      "    20EO/20PO 2363                                   17      "        "      H    200EO     9109                                   ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                                                             Average                                  Run                                  Molecular                                Number R.sub.1     R.sub.2                                                                             R.sub.3                                                                              R.sub.4 R.sub.5                                                                    Weight                                   ______________________________________                                        18     CH.sub.3 SO.sub.2                                                                         Cl    H      CH.sub.3                                                                           337                                      19     "           "     CH.sub.3                                                                             CH.sub.3                                                                           351                                      20     "           "     H      2EO  397                                      21     "           "     CH.sub.3                                                                             "    411                                      ______________________________________                                    

EXAMPLE 2

Fifteen milliliters of 2N sodium carbonate (0.03 moles) were mixed with15 milliliters of water. Five and nineteen hundredths parts ofsulfanilic acid (0.03 moles) and 30 milliliters of 1N sodium nitrite(0.03 moles) wre then added to the solution. In a separate vessel 37.5milliliters of 2N hydrochloric acid (0.075 moles) and 30 parts ice weremixed. This mixture was cooled to between 5° and 10° C. The sodiumcarbonate/water/sulfanilic acid/ sodium nitrite mixture was added slowlywith stirring to the cool hydrochloric acid solution. The temperatureduring the addition did not exceed 10° C. The mixture containing a whiteprecipitate was allowed to react for 5 minutes with continued cooling.Sulfamic acid was then added to destroy excess nitrite as monitored bystarch-iodide paper.

A mixture of the ten mole ethoxylate of aniline (0.035 moles) and 50parts of water was added slowly to the diazo mixture prepared abovewhile controlling the temperature between 5° and 10° C. The mixture wasallowed to stand for at least one hour after addition was complete. Thereaction mixture was then neutralized with 50% aqueous sodium hydroxideand the solvent removed under reduced pressure. Twenty milliliters ofisopropanol was added to the residue and the mixture allowed to heat atreflux for 5 minutes. This mixture was then filtered to remove unwantedsalts. The solvent was then removed from the filtrate under reducedpressure to afford the desired product.

A series of colorants were prepared using the preparation describedabove for use in generating the comparative data set forth in Examples10 and 15 as to the significance of the presence of an ionic group onthe chromophore. The colorants which had the following general structurewere prepared: ##STR4##

The colorants prepared in this manner are listed in Table 3 below. Allthe colorants listed in this table were obtained as liquids.

                  TABLE 3                                                         ______________________________________                                                                               Average                                Run                                    Molecular                              Number R.sub.1   R.sub.2                                                                              R.sub.3                                                                            R.sub.4 R.sub.5                                                                         Weight                                 ______________________________________                                        1      SO.sub.3.sup.- Na.sup.+                                                                 H      H    4EO        452                                   2      "         "      "    2EO/4PO    598                                   3      "         "      "    2EO/6PO    714                                   4      "         "      CH.sub.3                                                                           2EO/6PO    728                                   5      "         "      "    10/EO      732                                   6      "         "      "    2/5/5      890                                   7      "         "      H    2EO/10PO   946                                   8      "         "      "    2/10/3    1078                                   9      "         "      CH.sub.3                                                                           2/10/3    1092                                   10     "         "      H    20EO      1158                                   11     "         "      CH.sub.3                                                                           20EO      1172                                   12     "         "      "    2/10/6    1224                                   13     "         "      H    2/15/5    1456                                   14     "         "      CH.sub.3                                                                           2/14/8    1544                                   15     "         "      "    20EO/20PO 2332                                   ______________________________________                                    

EXAMPLE 3

Five tenths grams (0.5) of the colorant described in Example 1 #20 wasdissolved in 15 milliliters of tetrahydrofuran. One drop of pyridine and0.27 grams of sodium carbonate were then added to this solution. 0.0025moles of the decanoyl chloride was then added and the resulting mixturewas heated gently in a steam bath. The progress of the reaction wasmonitored by use of thin layer chromatography. After the reaction wascomplete the tetrahydrofuran was boiled off in a steam bath and theresulting waxy solid dissolved in 50 milliliters of methylene chloride.The methylene chloride solution was washed with equal volumes of water,5% aqueous sodium bicarbonate, and water again. The methylene chloridewas then removed under reduced pressure to afford the desired product.

A series of colorants were prepared for use in obtaining the comparativedata set forth in Example 10 as to the effect of substituting an alkylsubstituent of equal molecular weight for the polyalkyleneoxysubstituent contained in the colorants used in the composition of thisinvention. A series of colorants of the following general structure wereprepared: ##STR5##

The colorants prepared by this procedure are listed in Table 4 below.

                  TABLE 4                                                         ______________________________________                                                                              Average                                 Run                                   Molecular                               Number  R.sub.1    R.sub.2                                                                              R.sub.3                                                                            R.sub.6 R.sub.7                                                                      Weight                                  ______________________________________                                        1       SO.sub.3.sup.- Na.sup.+                                                                  H      H    CH.sub.3                                                                             482                                     2       SO.sub.2 CH.sub.3                                                                        Cl     "    C.sub.3 H.sub.7                                                                      538                                     3       "          "      "    C.sub.9 H.sub.19                                                                     706                                     ______________________________________                                    

EXAMPLE 4

One hundred sixty grams of the 10 mole ethoxylate of aniline was heatedwith 60 grams of sulfamic acid under nitrogen at 140° C. for 6 hours.The resulting product was cooled and diluted with 50 milliliters ofmethanol. The excess sulfamic acid was removed by filtration. Thefiltrate was neutralized with 48 grams of 50% aqueous sodium hydroxideand the excess water, methanol and ammonia removed under reducedpressure. The resulting glassy solid was liquified by addition of 100grams of water. This intermediate material was then converted to acolorant, having an average molecular weight of 953, of the followingstructure by use of the method described in Example 2. ##STR6##

This material was used to generate comparative date as set forth inExamples 10 and 15 as to the effect of end groups on the performance ofthe colorants in thermoplastic resin compositions.

EXAMPLE 5

Using the procedure set forth in Example 3, 0.00125 mole of the colorantdescribed in Table 1 #14 was allowed to react with 0.0025 mole of acetylchloride to afford the following product which was determined to have anaverage molecular weight of 1571. ##STR7##

This colorant was used to generate comparative data as set forth inExample 10 below to further demonstrate the effect on end groupsubstitutions on the colorants used in the composition of thisinvention.

EXAMPLE 6

Using the procedure described in U.S. Pat. No. 4,137,243, Example 1(incorporated by reference), a series of colorants of the followinggeneral structure were prepared from quinizarin and the appropriatepolyalkyleneoxy aliphatic amine. The colorants prepared in this mannerwere obtained as liquids and are listed in Table 5 below. ##STR8##

These colorants and those described in Examples 7, 8 and 9 below wereprepared to demonstrate the possibility for use of a wide range ofchromophore groups in preparing the colorants used in the composition ofthis invention.

                  TABLE 5                                                         ______________________________________                                                                            Average                                   Run                                 Molecular                                 Number  R.sub.8    R.sub.9    R.sub.10                                                                            Weight                                    ______________________________________                                        1       CH.sub.2 CH.sub.2 CH.sub.3                                                               2EO        OH     530                                      2       CH.sub.2 CH(CH.sub.3)                                                                    2PO        C.sub.11 H.sub.23                                                                    804                                      3       "          2PO/4EO    C.sub.4 H.sub.9                                                                      924                                      4       "          9PO/1EO    CH.sub.3 O                                                                          1404                                      5       "          3PO/19EO   "     2204                                      6       "          32PO/3EO   "     4204                                      ______________________________________                                    

EXAMPLE 7

Using the procedure described in Example 1, a series of colorants of thefollowing general structure were prepared by coupling the diazonium saltof 2-amino-6-methoxybenzothiazole with the appropriate polyalkyleneoxyaniline. ##STR9##

The colorants prepared by this procedure were obtained as liquids andare listed in Table 6 below.

                  TABLE 6                                                         ______________________________________                                        Run                    Average                                                Number       R.sub.4 R.sub.5                                                                         Molecular Weight                                       ______________________________________                                        1            4EO       460                                                    2            10EO      724                                                    3            2EO/8PO   836                                                    4            20EO      1164                                                   ______________________________________                                    

EXAMPLE 8

Using the procedure described in U.S. Pat. No. 4,507,407, Example 1(incorporated by reference), a series of colorants of the followinggeneral structure were prepared by coupling the diazonium salt of2-amino-3,5-dicyano-4-methyl thiophene with the appropriatepolyalkyleneoxy aniline. ##STR10##

The colorants prepared by this procedure were obtained as liquids andare listed in Table 7 below.

                  TABLE 7                                                         ______________________________________                                        Run                    Average                                                Number       R.sub.4 R.sub.5                                                                         Molecular Weight                                       ______________________________________                                        1            10EO      707                                                    2            2EO/8PO   819                                                    3            20EO      1147                                                   ______________________________________                                    

EXAMPLE 9

1-(p-tolyl)-3-methyl-5-pyrazalone and the ten mole ethoxylate ofp-aminobenzaldehyde were mixed in equal molar amounts and heated at 110°C. The progress of the reaction was monitored by observing thedisappearance of the ultraviolet absorbence peak at 341 nanometers.Heating was continued until this peak had disappeared. No furtherwork-up was required. Colorants of the following general structure wereprepared. ##STR11##

The colorants prepared were obtained as liquids and are listed in Table8 below.

                  TABLE 8                                                         ______________________________________                                        Run                   Average                                                 Number        R.sub.4 R.sub.5                                                                       Molecular Weight                                        ______________________________________                                        1              5EO    511                                                     2             10EO    731                                                     3             15EO    951                                                     4             20EO    1171                                                    ______________________________________                                    

EXAMPLE 10

Tests were conducted to determine the extractability of colorantsprepared according to Examples 1 through 9 above from polypropylenehomopolymer. First the color value of the colorants to be tested wasdetermined using the procedure detailed in Example Number 9 of U.S. Pat.No. 4,507,407 (incorporated by reference). Several commerciallyavailable dyestuffs reported to have utility in coloring certainthermoplastic resins were included in this study for comparativepurposes. In order to correct for differences in color strength amongthe colorants, the weight of each colorant used was adjusted accordingto its color value by use of the following formula:

    22.9/color value=weight used

The proper weight of the colorant to be tested was added to 1000 gramsof Hercules Profax 6301 polypropylene homopolymer pellets. The mixturewas then drum tumbled for 20 minutes to ensure uniform colorantdistribution over the surface of the pellets. In cases where thecolorant was a solid or semi-solid, it was first dissolved in theminimum amount of methanol necessary to produce a uniform solution andwas then added to the resin pellets. The colored pellets were theninjection molded at 428° F. into 3 inch by 2 inch plaques with abi-level thickness of 50 mils and 85 mils.

These plaques were then placed in a Soxlet extraction apparatus andextracted with acetone for eight hours. The extracts were then eachconcentrated to a volume of 100 milliliters and the absorbance of theextracts was determined using a Beckman DU-7 spectrometer. Thespectrometer was zeroed using the extract of an uncolored plaque and themaximum absorbance between 400 and 700 nanometers was recorded. Thepercent colorant extracted was then calculated using the followingformula: ##EQU1## where CW is the weight of colorant in the plaque. Thisnumber was obtained by multiplying the weight of the plaque by theamount of colorant used per one gram of resin.

Tables 9 and 10 demonstrate the effect of the composition of thepolyalkylene substituent and molecular weight on the extractability ofthe colorants.

                  TABLE 9                                                         ______________________________________                                                                      Weight                                                                              Col-                                                         Average    Per   or                                                EO/PO      Molecular  1000 g                                                                              Val- % Ex-                                Colorant                                                                              Content    Weight     Resin ue   tracted                              ______________________________________                                        Ex. 1 #1                                                                              4EO        485        0.42  54.3 3.5                                  Ex. 1 #2                                                                              2EO/2PO    513        0.43  53.1 2.6                                  Ex. 1 #3                                                                              2EO/4PO    629        0.49  47.2 2.3                                  Ex. 1 #4                                                                              2EO/6PO    745        0.61  37.6 1.7                                  Ex. 1 #5                                                                              10EO       749        0.58  39.8 0.9                                  Ex. 1 #6                                                                              10EO       763        0.54  42.3 1.1                                  Ex. 1 #7                                                                              2EO/8PO    861        0.67  34.4 1.3                                  Ex. 1 #8                                                                              2/5/5      921        0.68  33.8 1.2                                  Ex. 1 #9                                                                              2EO/10PO   977        0.80  28.8 1.2                                  Ex. 1 #10                                                                             2/10/3     1109       0.90  25.6 0.8                                  Ex. 1 #11                                                                             20EO       1122       1.52  15.0 0.5                                  Ex. 1 #12                                                                             2/10/3     1123       0.82  27.8 1.0                                  Ex. 1 #13                                                                             2/10/6     1255       1.00  22.9 0.8                                  Ex. 1 #14                                                                             2/15/5     1487       1.08  21.2 1.1                                  Ex. 1 #15                                                                             2/14/8     1575       1.18  19.5 1.2                                  Ex. 1 #16                                                                             20EO/20PO  2363       1.94  11.8 0.2                                  Ex. 1 #17                                                                             200EO      9109       13.63  1.7 0.2                                  ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                                         Average   Weight Per                                                EO/PO     Molecular 1000 g  Color % Ex-                                Colorant                                                                             Content   Weight    Resin   Value tracted                              ______________________________________                                        Ex. 6 #1                                                                             4EO       530       1.53    15.0  1.6                                  Ex. 6 #2                                                                             4PO       804       1.80    12.7  5.9                                  Ex. 6 #3                                                                             4PO/8EO   924       1.90    12.1  3.2                                  Ex. 6 #4                                                                             18PO/2EO  1404      3.09     7.4  1.9                                  Ex. 6 #5                                                                             6PO/38EO  2204      4.87     4.7  1.2                                  Ex. 6 #6                                                                             64PO/6EO  4204      9.96     2.3  1.0                                  Ex. 7 #1                                                                             4EO       460       0.26    89.9  3.8                                  Ex. 7 #2                                                                             10EO      724       0.40    57.2  1.4                                  Ex. 7 #3                                                                             2EO/8PO   836       0.45    50.8  2.2                                  Ex. 7 #4                                                                             20EO      1164      0.67    34.3  0.8                                  Ex. 8 #1                                                                             10EO      707       0.47    49.1  0.8                                  Ex. 8 #2                                                                             2EO/8PO   819       0.52    44.5  1.6                                  Ex. 8 #3                                                                             20EO      1147      0.77    29.1  0.4                                  Ex. 9 #1                                                                             5EO       511       0.36    64.0  5.0                                  Ex. 9 #2                                                                             10EO      731       0.60    38.6  2.5                                  Ex. 9 #3                                                                             15EO      951       0.75    30.5  1.9                                  Ex. 9 #4                                                                             20EO      1171      1.02    22.4  1.7                                  ______________________________________                                    

It is evident from this data that polyalkyleneoxy substituentscontaining a relatively higher percentage of the more hydrophilicethyleneoxy groups tend to perform better with respect tonon-extractability and that increasing molecular weight does tend toimprove non-extractability characteristics.

Table 11 shows the performance of conventional polymer soluble dyes withrespect to solvent extraction under the same conditions as above.

                  TABLE 11                                                        ______________________________________                                                    EO/PO    Weight Per       % Ex-                                   Colorant    Content  1000 g Resin                                                                             Color tracted                                 ______________________________________                                        Ex. 1 #18   --       0.36       Orange                                                                              19.9                                    Ex. 1 #19   --       0.35       "     20.4                                    Solvent Red 135                                                                           --       1.00       Red    5.7                                    Solvent Blue 130                                                                          --       0.40       Blue  14.9                                    Solvent Yellow 141                                                                        --       0.70       Yellow                                                                              16.1                                    ______________________________________                                    

As can be readily seen, these non-polyalkyleneoxy containing colorantsdo not perform as well with respect to non-extractability as do thepolyalkyleneoxy colorants.

Table 12 shows a comparison between polyalkyleneoxy containing colorantsand alkyl derivatives of similar structure and molecular weight whenextracted under the conditions of this test.

                  TABLE 12                                                        ______________________________________                                                                   Weight                                                              Average   Per                                                       EO/PO     Molecular 1000 g                                                                              Color %                                      Colorant                                                                             Content   Weight    Resin Value Extracted                              ______________________________________                                        Ex. 1 #2                                                                             2 EO/2 PO 513       0.43  53.1  2.6                                    Ex. 3 #2                                                                             alkyl     538       0.61  37.6  12.5                                   Ex. 1 #5                                                                             10 EO     749       0.58  39.8  0.9                                    Ex. 3 #3                                                                             alkyl     706       0.56  40.9  7.4                                    ______________________________________                                    

It can be seen that those colorants containing polyalkyleneoxysubstituents perform far better than colorants of equivalent molecularweight containing alkyl substituents under the conditions of this test.

Table 13 demonstrates the effect of various end groups on the colorantextractability. Under the conditions of this test, there was nodependence observed of extractability on end group composition.

                  TABLE 13                                                        ______________________________________                                                EO/PO     End       Weight Per                                                                             %                                        Colorant                                                                              Content   Group     1000 g Resin                                                                           Extracted                                ______________________________________                                        Ex. 1 #5                                                                              10 EO     OH        0.58     1.0                                      Ex. 3   10 EO     SO.sub.3.sup.- Na.sup.+                                                                 0.92     0.8                                      Ex. 1 #14                                                                             2/15/5    OH        1.08     1.1                                      Ex. 4   2/15/5    Ac        1.15     0.9                                      ______________________________________                                    

Finally, under the conditions of this test, the anionic colorantsdescribed in Example 2 gave no measurable extract which indicates thatchromophoric groups of this nature may be very advantageous.

EXAMPLE 11

The test defined in Example 10 was repeated using Dow Chemical Dowlex2517 linear low density polyethylene as the thermoplastic resin. Thecolorants tested were those contained in Table 14 below which shows acomparison between conventional polymer-soluble dyes and the colorantsused in this invention. The extractions were limited to 4 hours.

                  TABLE 14                                                        ______________________________________                                                   EO/PO    Weight Per       %                                        Colorant   Content  1000 g Resin                                                                             Color Extracted                                ______________________________________                                        Ex. 1 #18  --       0.36       Orange                                                                              36.0                                     Ex. 1 #19  --       0.35       "     49.4                                     Ex. 1 #13  2/10/6   1.00       "      3.0                                     Solvent Red 135                                                                          --       1.00       Red   20.2                                     Ex. 8 #3   20 EO    0.79       Violet                                                                               1.9                                     Solvent Blue 130                                                                         --       0.40       Blue  41.0                                     ______________________________________                                    

After setting for two weeks at ambient temperatures, the plaquescontaining the non-polyalkyleneoxy-substituted colorants developed avisible layer of colorant on their surface which was easily rubbed off.The plaques containing the polyalkyleneoxy-substituted colorants showedno visible change in appearance.

EXAMPLE 12

The test defined in Example 10 was repeated using USI ChemicalPetrothene N208 low density polyethylene as the thermoplastic resin. Thecolorants tested were those contained in Table 15 below. The extractionswere carried out for 8 hours. Again, a comparison to conventionalpolymer-soluble dyes is included.

                  TABLE 15                                                        ______________________________________                                                    EO/PO    Weight Per       % Ex-                                   Colorant    Content  1000 g Resin                                                                             Color tracted                                 ______________________________________                                        Ex. 1 #18   --       0.36       Orange                                                                              52.9                                    Ex. 1 #19   --       0.35       "     80.3                                    Ex. 1 #13   2/10/6   1.00       "      2.5                                    Solvent Red 135                                                                           --       1.00       Red   46.2                                    Ex. 9 #4    20 EO    1.02       Yellow                                                                               3.7                                    Solvent Yellow 141                                                                        --       0.7        "     51.1                                    ______________________________________                                    

As in Example 11, there was visible evidence of dye migration on thoseplaques containing the conventional polymer-soluble dyes which was notpresent on those plaques colored with the polyalkyleneoxy containingcolorants.

EXAMPLE 13

The test defined in Example 10 was repeated using Amoco high densitypolyethylene as the thermoplastic resin. The colorants tested were thosecontained in Table 16 below. The extractions were carried out for 8hours. Again, several conventional polymer-soluble dyes are included forcomparison.

                  TABLE 16                                                        ______________________________________                                                   EO/PO    Weight Per       %                                        Colorant   Content  1000 g Resin                                                                             Color Extracted                                ______________________________________                                        Ex. 1 #18  --       0.36       Orange                                                                              29.4                                     Ex. 1 #19  --       0.35       "     23.5                                     Ex. 1 #13  2/10/6   1.00       "      0.3                                     Solvent Red 135                                                                          --       1.00       Red   16.7                                     Ex. 7 #4   20 EO    0.67       "      0.4                                     ______________________________________                                    

EXAMPLE 14

The test defined in Example 10 was repeated using Hercules Profax SA-841polypropylene copolymer as the thermoplastic resin. The number ofcolorants tested were those contained in Table 17 below. The extractionswere carried out for 8 hours. Several conventional polymer-soluble dyesare included for comparison.

                  TABLE 17                                                        ______________________________________                                                   EO/PO    Weight Per       %                                        Colorant   Content  1000 g Resin                                                                             Color Extracted                                ______________________________________                                        Ex. 1 #18  --       0.36       Orange                                                                              50.3                                     Ex. 1 #19  --       0.35       "     50.4                                     Ex. 1 #13  2/10/6   1.00       "     7.0                                      Solvent Red 135                                                                          --       1.00       Red   9.4                                      Ex. 6 #1   --       1.00       Blue  3.6                                      ______________________________________                                    

EXAMPLE 15

The test defined in Example 10 was repeated using B. F. Goodrich Geon83457 flexible polyvinylchloride as the thermoplastic resin. Thecolorants tested were those contained in Table 18 below. The extractionswere carried out for 4 hours with hexane inplace of acetone. The hexanewas then removed from the extract and the extract was then dissolved in100 milliliters of methanol. This methanol solution was then read on thespectrometer. Several conventional non-polyalkyleneoxy-containing dyesare included for comparison.

                  TABLE 18                                                        ______________________________________                                                    EO/PO    Weight Per       % Ex-                                   Colorant    Content  1000 g Resin                                                                             Color tracted                                 ______________________________________                                        Ex. 1 #13   2/10/6   1.00       Orange                                                                              2.9                                     Ex. 2 #5    10 EO    0.72       "     0.6                                     Ex. 7 #4    20 EO    0.67       Red   0.8                                     Solvent Red 135                                                                           --       1.00       "     47.6                                    Ex. 8 #3    20 EO    0.79       Violet                                                                              1.8                                     Ex. 6 #1     4 EO    1.00       Blue  3.1                                     Solvent Blue 130                                                                          --       0.40       Blue  32.5                                    Ex. 9 #4    20 EO    1.02       Yellow                                                                              2.7                                     Solvent Yellow 141                                                                        --       0.70       Yellow                                                                              19.7                                    Ex. 4       10 EO    0.92       "     0.9                                     ______________________________________                                    

As in Examples 11 and 12 the plaques colored with the conventional dyesshowed visible evidence of migration of the colorant to the surfacewhereas none was evident on the plaques colored with the polyalkyleneoxycontaining colorants.

EXAMPLE 16

The test defined in Example 10 was repeated using Eastman TeniteButyrate 264E-37200-MH cellulose acetate butyrate as the thermoplasticresin. The number of colorants tested was limited to those contained inTable 19 below. The extractions were carried out for 8 hours with hexanein place of acetone. The hexane was removed from the extract, and theextract was then dissolved in 100 milliliters of methanol. This methanolsolution was then read on the spectrometer.

                  TABLE 19                                                        ______________________________________                                                    EO/PO    Weight Per       % Ex-                                   Colorant    Content  1000 g Resin                                                                             Color tracted                                 ______________________________________                                        Ex. 1 #13   2/10/6   1.00       Orange                                                                              0.1                                     Ex. 7 #4    20 EO    0.67       Red   0.0                                     Solvent Red 135                                                                           --       1.00       "     5.0                                     Ex. 8 #3    20 EO    0.79       Violet                                                                              0.4                                     Ex. 6 #1     4 EO    1.00       Blue  0.0                                     Solvent Blue 130                                                                          --       0.40       "     6.5                                     Ex. 9 #4    20 EO    1.02       Yellow                                                                              0.4                                     Solvent Yellow 141                                                                        --       0.70       "     4.4                                     ______________________________________                                    

EXAMPLE 17

A mixture of 9960 grams of Hercules Profax 6501 polypropylenehomopolymer, 10 grams of Irganox 1010 from Ciba Geigy, 10g of calciumstearate and 20 grams of Millad 3940 clarifying agent from MillikenChemical was blended and then extruded at 400° F. To 1000 grams of thepelletized resin was added 1.0 gram of the colorant prepared in Example1 #17. The resulting mixture was then drum tumbled for 20 minutes untilan even distribution of the colorant on the pellet surface was achieved.The mixture was then injection molded at 428° F. into 2 in. by 3 in.plaques having a by-level thickness of 50 and 85 mils. The plaquesobtained were uniformly colored and had excellent clarity. A haze valueof 19% was obtained.

EXAMPLES 18-24

The polyalkyleneoxy-substituted colorants described in the previousexamples were incorporated into a wide variety of thermoplastic resinsto demonstrate the broad utility of the invention. The followingprocedure was used. To 1000 grams of the thermoplastic resin (pellets orcrystals) was added 1.0 gram of a polyalkyleneoxy-substituted colorantdescribed in the previous examples. This mixture was then drum tumbledfor 20 minutes to achieve uniform distribution of the colorant on thesurface of the resin. The mixture was then injection molded into 3 in.by 2 in. plaques at a temperature reported in Table 20 below forprocessing the particular resin. In this manner there was obtainedbrightly colored plaques which had excellent color uniformity. Thecolorants had little or no detrimental effect on the clarity of theseresins; and in instances where the uncolored resin is normally clear,the colored resins exhibited excellent clarity. The resins and colorantsused are listed in Table 20.

                  TABLE 20                                                        ______________________________________                                                                  Molding                                             Ex.                       Temper-                                             No.  Resin                ature    Colorant                                   ______________________________________                                        18   Monsanto Lustrex Polystyrene                                                                       400° F.                                                                          Ex. 1, #17                                19   Rohm & Haas Plexiglas Acrylic                                                                      430° F.                                                                         Ex. 8, #4                                  20   Celanese Celanex J245                                                                              500° F.                                                                         Ex. 6, #1                                       Polybutylene Terephthalate                                               21   Allied Capron 8202 Nylon                                                                           500° F.                                                                         Ex. 7, #4                                  22   Mobay Merlon M40HRF-1112                                                                           560° F.                                                                          Ex. 1, #17                                     Polycarbonate                                                            23   Monsanto Lustran 248-1002                                                                          430° F.                                                                         Ex. 9, #4                                       Acrylonitrile/Butadiene/Styrene                                          24   Eastman Kodar PETG Copolyester                                                                     460° F.                                                                          Ex. 1, #17                                     Glycol Modified Polyethylene                                                  Terephthalate                                                            ______________________________________                                    

EXAMPLE 25 Preparation of Thermoplastic Resin Inks Containing PolymericColorants

Five parts of a thermoplastic cellulose ester resin, Eastman CAP504-0.2,purchased from Eastman Chemical Company were dissolved in 15 parts ofmethanol to give a clear viscous solution. One-half part of a polymericcolorant of the formula: ##STR12## was mixed with the viscous solutionto provide a dark blue solution. It was found that this solutionfunctioned as an ink for the purposes of writing on glass to provide awet crock stable image.

EXAMPLE 26

To the solution prepared as described in Example 25, an additional 0.5part of the colorant described in Example 25 was added followed by 15parts acetone. This solution was loaded into a drawing marker with aporous composite tip and the marker was used to write on glass andtransparency sheets providing wet crock stable images.

EXAMPLE 27 Preparation of Toluene Thermoplastic Resin Inks for PaperPrinting

To six parts of a Publication Gravure rosin acid salt varnish purchasedfrom Flint Ink (DS-914), was added .85 part blue colorant as describedin Example 25 and .15 part of a violet colorant of the formula:##STR13## and two parts toluene. The solution was mixed to provide astable blue ink. Draw down comparisons on paper using a Hegman knifewere made between the blue ink prepared as described herein and thestandard ink Publication Gravure "Process Blue". Approximately equalcolor depth was observed with the blue ink prepared as described hereinbeing slightly brighter in color. Slight wet crock was observed for theblue ink as described herein. Similar ink compositions were prepared tothe blue ink as described herein using polymeric yellow, red, orange andviolet colorants. All such ink compositions showed similar color depth,brightness and wet crock characteristics.

EXAMPLE 28

Cellulose acetate butyrate purchased from Eastman and described inExample 16 above was dissolved in acetone to give 7.1 weight percentpolymer in the acetone solution. A series of colorant solutionsemploying colorants as described in Table 19 above were prepared inacetone by dissolving the respective colorants (22.9/color value)milligrams of colorant per gram of acetone. One part of the colorantsolution was mixed with 14 parts of polymer solution to provide a clear,colored solution. Fifteen grams of this solution was pured into analuminum weighing dish and the solvent was allowed to evaporateovernight at room temperature. The resulting colored polymer castingswere placedin an oven at 100° C. for one hour to remove residualsolvent. Hard, colored discs containing some entrapped bubbles wereobtained.

EXAMPLE 29

One part polystyrene having an average molecular weight of 250,000(Aldrich 18,242-7) was dissolved in five parts toluene. One part of therespective colorant solutions described in Example 28 above were mixedwith six parts of the polystyrene solution to provide a clear coloredsolution. Seven grams of this solution were placed in an aluminumweighing dish and treated as in Example 28 to give clear colored polymercastings.

EXAMPLE 30

Samples of the polymer castings prepared in Examples 28 and 29 aboveweighing .24 and 1.0 grams respectively were placed in glass vials,sealed, and extracted using hexane and isopropyl alcohol solvents for 20hours at 60° C. The samples were cooled and the absorbance of thesolvents was measured spectrophotometricly. Percent extraction wascalculated based upon the weight of polymer casting extracted using theformula: ##EQU2## The results of these tests are summarized in Tables 21and 22.

                                      TABLE 21                                    __________________________________________________________________________    Extraction Studies From Cellulose Acetate Butyrate                                               Weight Per      Percent Extracted                                      EO/PO  1,000 Grams                                                                          Percent Extracted                                                                      (As reported in                            Colorant    Content                                                                              Resin  (Hexane Solvent)                                                                       Example 16 above)                          __________________________________________________________________________    EX. 1 #13   2/10/6 1.0    0.4      0.1                                        AS IN EX. 1 NO. 13                                                                        DIMETHYL                                                                             0.27   1.9      --                                         EX. 6 #2    10 EO  0.42   0.0      --                                         AS IN EX. 6 #2                                                                             2 EO  0.22   0.0      --                                         EX. 8 #3    20 EO  0.8    0.0      0.4                                        SOLVENT BLUE                                                                              --     0.4    6.5      6.5                                        130                                                                           SOLVENT YELLOW                                                                            --     0.7    1.0      4.4                                        141                                                                           SOLVENT RED 135                                                                           --     1.0    3.4      5.0                                        EX. 9 #4    20 EO  1.0    0.2      0.4                                        AS IN EX. 9 #4                                                                            DIMETHYL                                                                             0.26   3.4      --                                         __________________________________________________________________________

As shown in Table 21 above, the extraction figures from celluloseacetate butyrate which has been prepared by first dissolving the resinin a suitable solvent and then incorporating the colorant into the resinare quite comparable to the results obtained by incorporating thecolorant into the molten polymer. Note also that Table 21 containsexamples of dimethyl dyes that extract 5 times more than their polymericcounterparts.

                  TABLE 22                                                        ______________________________________                                        Extraction Studies From Polystyrene                                                                                Percent                                                               Percent Extracted                                                  Weight Per Extracted                                                                             (Isopropyl                                       EO/PO     1,000 Grams                                                                              (Hexane Alcohol                                  Colorant                                                                              Content   Resin      Solvent)                                                                              Solvent)                                 ______________________________________                                        EX. 1 #13                                                                             2/10/6    1.0        33.0    1.5                                      AS IN   DI-        0.27      43.8    6.1                                      EX. 1 #13                                                                             METHYL                                                                EX. 6 #2                                                                              10EO       0.42      5.7     2.4                                      AS IN    2EO       0.22      2.4     6.6                                      EX. 6 #2                                                                      EX. 8 #3                                                                              20EO      0.8        3.0     1.6                                      SOLVENT --        0.4        42.7    3.8                                      BLUE 130                                                                      SOLVENT --        0.7        62.7    25.5                                     YELLOW                                                                        141                                                                           SOLVENT --        1.0        17.5    3.4                                      RED 135                                                                       EX. 9 #4                                                                              20EO      1.0        1.3     1.9                                      AS IN   DI-        0.26      41.3    7.6                                      EX. 9 #4                                                                              METHYL                                                                ______________________________________                                    

What is claimed is:
 1. A colored thermoplastic resin composition whichcomprises a thermoplastic resin and a colorant in the form of apolyalkyleneoxy-substituted chromophore group incorporated into saidthermoplastic resin in a minor amount sufficient to provide coloration,while said thermoplastic resin is dissolved in a solvent so as todistribute said colorant throughout the mass of said thermoplastic resinand thereafter said solvent is evaporated so that said colorant isessentially non-extractable from said resin.
 2. The colored resincomposition of claim 1, wherein the chromophore group is selected fromnitroso, nitro, azo, diarylmethane, triarylmethane, xanthene, acridene,quinoline, methine, thiazole, indamine, indophenol, lactone,aminoketone, hydroxyketone, stilbene, azine, oxazine, thiazine,anthraquinone, phthalocyanine or indigoid chromophore groups.
 3. Thecolored resin composition of claim 2, wherein the alkyleneoxysubstituent of said colorant is selected from polyalkylene oxides andcopolymers of polyalkylene oxides in which the alkylene moiety of thepolymeric substituent contains 2 to about 4 carbon atoms and suchpolymeric substituent has a molecular weight of from about 132 to about10,000.
 4. The colored resin composition of claim 1 wherein said resinis selected from polyolefin polymers and copolymers, polystyrenes,polycarbonates, ABS, polyvinyl chloride, polyvinylidene choloride,cellulosic resins, acrylic resins, polyamides and polyesters.
 5. Thecolored resin composition of claim 4 wherein said resin is a polyolefin.6. The resin of claim 5 wherein said polyolefin is selected frompolyethylene, linear low density polyethylene, polypropylene,polybutylene and copolymers made from ethylene, propylene and/orbutylene.
 7. A colored thermoplastic resin composition which comprises athermoplastic resin selected from polyvinyl chloride and polyvinylidenechloride and a colorant in the form of polyalkyleneoxy-substitutedchromophore group incorporated in said thermoplastic resin in a minoramount sufficient to provide coloration, while said thermoplastic resinis dissolved in a solvent so as to distribute said colorant throughoutthe mass of said thermoplastic resin and thereafter said solvent isevaporated so that said colorant is essentially non-extractable fromsaid resin.
 8. The colored resin composition of claim 1 wherein saidchromophore group is selected from azo, anthraquinone, triaryl methaneand methine chromophore groups.
 9. The color resin composition of claim5 which further contains a clarifying agent selected from dibenzylidenesorbitols and substituted dibenzylidene sorbitols in an amountsufficient to improve the clarity of said thermoplastic polyolefinresin.
 10. A process for coloring a thermoplastic resin which comprisesincorporating into said resin while said resin is dissolved in asolvent, a colorant in the form of a polyalkyleneoxy-substitutedchromophore group in a minor amount sufficient to provide coloration tosaid thermoplastic resin and thereafter evaporating said solvent toprovide a colored thermoplastic resin product.
 11. The process of claim10 wherein said chromophore group is selected from nitroso, nitro, azo,diarylmethane, triarylmethane, xanthene, acridene, quinoline, methine,thiazole, indamine, indophenol, lactone aminoketone, hydroxyketone,stilbene, azine, oxazine, thiazine, anthraquinone, phthalocyanine orindigoid chromophore groups.
 12. The process od claim 11 wherein thealkyleneoxy substituent of said colorant is selected from polyalkyleneoxides and copolymers of polyalkylene oxides in which the alkylenemoiety of the polymeric substituent contains 2 to about 4 carbon atomsand such polymeric substituent has a molecular weight of from about 132to about 10,000.
 13. The process of claim 10 wherein said resin isselected from polyolefin polymers and copolymers, polystyrenes,polycarbonates, ABS, polyvinyl chloride, polyvinylidene chloride,cellulosic resins, acrylic resins, polyamides and polyesters.
 14. Theprocess of claim 13 wherein said resin is a polyolefin.
 15. The processof claim 14 wherein said polyolefin is selected from polyethylene,linear low density polyethylene, polypropylene, polybutylene, andcopolymers made from ethylene, propylene and/or butylene.
 16. Theprocess of claim 13 wherein said resin is selected frompolyvinylchloride and polyvinylidene chloride.
 17. The process of claim13 wherein said chromophore group is selected from azo, anthraquinone,triarylmethane and methine groups.